CN109876858B - Preparation method of (methyl) acrylate substance and application of 2-acrylamide-2-methylpropanesulfonic acid - Google Patents

Preparation method of (methyl) acrylate substance and application of 2-acrylamide-2-methylpropanesulfonic acid Download PDF

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CN109876858B
CN109876858B CN201910033294.0A CN201910033294A CN109876858B CN 109876858 B CN109876858 B CN 109876858B CN 201910033294 A CN201910033294 A CN 201910033294A CN 109876858 B CN109876858 B CN 109876858B
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esterification reaction
alcohol
methyl
acrylamide
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CN109876858A (en
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张春华
庞来兴
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Guangdong Boxing New Materials Technology Co ltd
Hubei Zhongke Bohong New Material Technology Co ltd
Zhang Chunhua
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Guangdong Bossin Novel Materials Technology Co Ltd
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Abstract

The invention relates to a preparation method of (methyl) acrylate substances and application of 2-acrylamide-2-methylpropanesulfonic acid. The 2-acrylamide-2-methylpropanesulfonic acid AMPS is used as a catalyst in esterification reaction. The research of the inventor of the invention finds that the 2-acrylamide-2-methylpropanesulfonic acid AMPS can be used as a catalyst for catalyzing esterification reaction, and has good catalytic activity and high yield. When the catalyst is applied to the preparation of (methyl) acrylate substances, the process is simple, the catalytic effect is good, and 2-acrylamide-2-methylpropanesulfonic acid and (methyl) acrylic acid are dissolved mutually in the esterification process, so that the esterification is favorably carried out. In addition, the solubility of the 2-acrylamide-2-methylpropanesulfonic acid at a lower temperature is lower, the temperature is reduced and the 2-acrylamide-2-methylpropanesulfonic acid is cooled after the esterification reaction, and the 2-acrylamide-2-methylpropanesulfonic acid is crystallized and separated out due to the reduction of the solubility, and can be recycled by filtration and separation.

Description

Preparation method of (methyl) acrylate substance and application of 2-acrylamide-2-methylpropanesulfonic acid
Technical Field
The invention relates to the technical field of esterification reaction, and more particularly relates to a preparation method of (methyl) acrylate substances and application of 2-acrylamide-2-methylpropanesulfonic acid.
Technical Field
Currently, it is a common practice to prepare (meth) acrylates by esterification. The esterification catalyst may be inorganic strong acid, organic sulfonic acid, solid acid, etc. The (methyl) acrylate substance is taken as the most common esterification reaction product, and can be widely applied to the fields of crosslinking curing materials, such as coatings, printing ink, adhesives, structural materials and the like of photocuring or electron beam curing (UV/EB). In the actual production of (meth) acrylate, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid are widely used in the preparation of (meth) acrylate due to their low cost, high catalytic activity, and the like. However, the esterification reaction is a reversible reaction, and (meth) acrylic acid is generally added in an excess amount in order to allow the reaction to proceed in the esterification direction as much as possible and to complete the reaction. After the reaction is finished, because the properties of the methanesulfonic acid, the p-toluenesulfonic acid and the sulfuric acid are close to those of the (meth) acrylic acid, the methanesulfonic acid, the p-toluenesulfonic acid and the sulfuric acid are difficult to separate and remove, the methanesulfonic acid, the p-toluenesulfonic acid and the sulfuric acid and the (meth) acrylic acid are generally removed at one time by adding alkaline substances for alkali washing, and a large amount of salt-containing waste liquid is generated at the time; in addition, in order to remove alkaline substances completely, a large amount of water is needed for washing for many times, the operation is complicated, the reaction process and the production period are prolonged, and a large amount of alkaline substances and water resources are needed to be input. In addition, methane sulfonic acid, p-toluenesulfonic acid and sulfuric acid cannot be recycled, unreacted (methyl) acrylic acid is wasted, salt-containing waste liquid needs to be treated and then can be discharged, and the treatment cost is high.
Therefore, the development of a novel catalyst which has high catalytic efficiency and can be recycled has important research significance and industrial application value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings in the prior art and provides application of 2-acrylamide-2-methylpropanesulfonic acid AMPS as a catalyst in esterification reaction. The research of the inventor of the invention finds that the 2-acrylamide-2-methylpropanesulfonic acid AMPS can be used as a catalyst for catalyzing esterification reaction, and has good catalytic activity and high yield. When the catalyst is applied to the preparation of (methyl) acrylate substances, the process is simple, the catalytic effect is good, and 2-acrylamide-2-methylpropanesulfonic acid and (methyl) acrylic acid are dissolved mutually in the esterification process, so that the esterification is favorably carried out. In addition, the solubility of the 2-acrylamide-2-methylpropanesulfonic acid at a lower temperature is lower, the temperature is reduced and the 2-acrylamide-2-methylpropanesulfonic acid is cooled after the esterification reaction, and the 2-acrylamide-2-methylpropanesulfonic acid is crystallized and separated out due to the reduction of the solubility, and can be recycled by filtration and separation.
The invention also aims to provide a preparation method of the (methyl) acrylic ester substances.
In order to achieve the purpose, the invention adopts the following technical scheme:
the application of 2-acrylamide-2-methyl propanesulfonic acid AMPS as a catalyst in esterification reaction.
The inventor of the invention researches and discovers that 2-acrylamide-2-methylpropanesulfonic acid AMPS can be used as a catalyst for catalyzing esterification reaction, and has good catalytic activity and high yield; and 2-acrylamide-2-methylpropanesulfonic acid and (methyl) acrylic acid are dissolved mutually in the esterification process, so that the esterification is facilitated. In addition, the solubility of the 2-acrylamide-2-methylpropanesulfonic acid at a lower temperature is lower, the temperature is reduced and the 2-acrylamide-2-methylpropanesulfonic acid is cooled after the esterification reaction, and the 2-acrylamide-2-methylpropanesulfonic acid is crystallized and separated out due to the reduction of the solubility, and can be recycled by filtration and separation. Even if 2-acrylamido-2-methylpropanesulfonic acid remains, it has the same acryloyl functional group as (meth) acrylate, and therefore has little effect on the use of (meth) acrylate.
Preferably, the raw materials of the esterification reaction are alcohols and monounsaturated acids.
Preferably, the using amount of the 2-acrylamide-2-methylpropanesulfonic acid AMPS is 0.5-10% of the sum of the mass of the alcohols and the mass of the monounsaturated acid.
More preferably, the using amount of the 2-acrylamide-2-methylpropanesulfonic acid AMPS is 1-5% of the sum of the mass of the alcohols and the mass of the monounsaturated acid.
The esterification reaction generally starts from an alcohol and a carboxylic acid, both of which are conventional in the art.
Preferably, the alcohol is a monohydric alcohol or a polyhydric alcohol; the monounsaturated acid is (meth) acrylic acid.
When (meth) acrylic acid is used as a reaction raw material, 2-acrylamido-2-methylpropanesulfonic acid has the same acryloyl functional group as that of (meth) acrylic acid esters, and even if it remains, it has little influence on the use of (meth) acrylic acid esters.
Both monohydric and polyhydric alcohols (e.g., dihydric, trihydric, tetrahydric, hexahydric, hyperbranched polyols, etc.) may be used in the present invention.
Preferably, the monohydric alcohol is lauryl alcohol, C8-C10One or more of alcohol, isooctanol, isodecanol, tetrahydrofuryl alcohol, cyclotrimethylolpropane formal, o-phenylphenoxy ethanol, 2- (2-hydroxyethoxy) phenol, diethylene glycol monoethyl ether, ethoxyethoxyethoxyethanol and ethoxynonylphenol.
Preferably, the polyol is ethylene glycol, neopentyl glycol, 1, 3-propanediol, 1, 6-hexanediol, 2-ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol (methylpropanediol), dipropylene glycol, tripropylene glycol, ethoxylated neopentyl glycol, propoxylated neopentyl glycol, ethoxylated-1, 6-hexanediol, 1, 4-butanediol, diethylene glycol, triethylene glycol, ethoxylated bisphenol A, propoxylated bisphenol A, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, diethylene glycol phthalate, polyethylene glycol, polypropylene glycol, polyester diol, polytetrahydrofuran glycol, polycaprolactone diol, trimethylolpropane, trimethylolethane, trimethylolpropane, or mixtures thereof, Ethoxylated trimethylolpropane, propoxylated trimethylolpropane, glycerol, ethoxylated glycerol, propoxylated glycerol, tris (2-hydroxyethyl) isocyanuric acid, tris (hydroxypropyl) isocyanuric acid, ethoxylated isocyanuric acid, propoxylated isocyanuric acid, caprolactone chain-extended ethoxylated isocyanuric acid, polyester triol, ditrimethylolpropane, ethoxylated ditrimethylolpropane, propoxylated ditrimethylolpropane, caprolactone chain-extended ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, propoxylated pentaerythritol, caprolactone chain-extended pentaerythritol, polyester tetraol, dipentaerythritol, ethoxylated dipentaerythritol, propoxylated dipentaerythritol, caprolactone chain-extended dipentaerythritol, polyester hexahydric alcohol, or hyperbranched polyester polyol.
Preferably, the monounsaturated acid is (meth) acrylic acid.
A method for preparing (methyl) acrylic ester substances comprises the following steps:
alcohol and (methyl) acrylic acid are used as raw materials, 2-acrylamide-2-methylpropanesulfonic acid AMPS is used as a catalyst, and a polymerization inhibitor and a solvent are added for esterification reaction.
2-acrylamide-2-methylpropanesulfonic acid AMPS is used as a catalyst, and can catalyze alcohols and (methyl) acrylic acid to carry out esterification reaction under conventional conditions to obtain (methyl) acrylate substances, so that the catalytic activity is good, and the yield is high; and after the esterification reaction is finished, cooling the esterification reaction system, and recovering 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) in a filtering manner, wherein the AMPS can be recycled.
Polymerization inhibitors and solvents (i.e., water-carrying agents) conventional in the art may be used in the present invention.
Preferably, the polymerization inhibitor is hydroquinone HQ, 4-methoxyphenol MEHQ, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2, 6-dimethylphenol, 2, 5-di-tert-butylphenol; one or more of copper chloride, cuprous chloride, copper oxide, cuprous oxide, basic copper carbonate, copper sulfate, copper acetate, acrylic acid ketone, copper methacrylate, copper salicylate, copper naphthenate, copper acetylacetonate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, cobalt acetate, cobalt carbonate, manganese acetate, manganese carbonate, manganese chloride, manganese sulfate, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, dibutyl phosphite, tricyclohexyl phosphite, hypophosphorous acid or phosphorous acid.
Preferably, the solvent is one or more of toluene, cyclohexane, n-hexane, methylcyclohexane, heptane or petroleum ether.
More preferably, the solvent is one or more of toluene, cyclohexane, methylcyclohexane or n-heptane.
Preferably, the temperature of the esterification reaction is 70-130 ℃.
More preferably, the temperature of the esterification reaction in S1 is 80-110 ℃.
Preferably, when the alcohol is a monohydric alcohol, the equivalent ratio of the hydroxyl group equivalents in the alcohol to (meth) acrylic acid is 1:1.1 ~ 1.5.5.
Preferably, when the alcohol is a polyol, the equivalent ratio of the hydroxyl group equivalent in the alcohol to (meth) acrylic acid is 1:0.8 ~ 1.3.3.
More preferably, when the alcohol is a polyol, the equivalent ratio of the hydroxyl group equivalent in the alcohol to (meth) acrylic acid is 1:0.9 ~ 1.15.15.
Preferably, oxygen-containing gas is introduced during the esterification reaction.
The introduction of gas containing oxygen can further improve the polymerization inhibiting effect, the gas can contain inactive gas besides oxygen, and the content of oxygen is limited by improving the polymerization inhibiting effect and preventing the reaction device from exploding.
More preferably, the gas further comprises one or more of nitrogen, helium or argon.
Preferably, the volume fraction of oxygen in the gas is 0.5-22%.
The esterification reaction may be, but is not limited to, carried out under negative pressure conditions.
Preferably, the absolute pressure of the esterification reaction is 20-80 KPa, and the esterification reaction temperature is 70-100 ℃.
Preferably, the esterification reaction also comprises cooling and filtering to recover the catalyst after the esterification reaction is finished; washing and recovering the polymerization inhibitor.
Preferably, the esterification reaction also comprises a step of recovering the solvent by distillation after the end of the esterification reaction.
Preferably, the temperature is cooled to below 40 ℃ and then filtered.
More preferably, the temperature is cooled to 30 ℃ or lower and then filtered.
Preferably, the filtering process is: filtering with closed filtering equipment.
Preferably, the esterification reaction process further comprises the steps of performing dehydration treatment to obtain acid water and a solvent, and returning the solvent to the esterification reaction system.
The acid water obtained after dehydration contains a small amount of (meth) acrylic acid, the concentration of which is generally 1 to 25%, and a reflux column is generally used for washing after esterification, and the acid concentration of which is 1 to 10%. Therefore, the principle of a small amount of times can be adopted, and the generated low-concentration acid water is washed for 3-6 times.
Preferably, after the esterification reaction, washing is performed using the acid water.
More preferably, the washing temperature is 30-80 ℃.
More preferably, the washing temperature in S2 is 40-60 deg.C
Preferably, the preparation method comprises the following specific processes: taking alcohols and (methyl) acrylic acid as raw materials, taking 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) as a catalyst, and adding a polymerization inhibitor and a solvent for esterification reaction; cooling, filtering and recovering the catalyst, washing and recovering the polymerization inhibitor, distilling and recovering the solvent, and adding the catalyst b, the polymerization inhibitor 2 and the epoxide for reaction.
Or the preparation method comprises the following specific processes: taking alcohols and (methyl) acrylic acid as raw materials, taking 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) as a catalyst, and adding a polymerization inhibitor and a solvent for esterification reaction; cooling, filtering to recover catalyst, washing to recover polymerization inhibitor, adding catalyst B, polymerization inhibitor 2 and epoxide to react, and distilling to recover solvent.
In the existing report and actual production, when the direct esterification reaction is carried out by the reaction of alcohols and (meth) acrylic acid, liquid strong acid or compatible strong acid such as sulfuric acid, methane sulfonic acid, p-toluenesulfonic acid is selected as a catalyst, and (meth) acrylic acid is excessively added, the catalyst and unreacted (meth) acrylic acid are difficult to separate after the esterification reaction is finished, an alkaline waste liquid is generally obtained by alkaline washing (washing with alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like), the catalyst and the (meth) acrylic acid are removed, and a large amount of water is needed for washing for multiple times to remove the alkaline substances added into the reaction product, so that the operation is complicated, the reaction process and the production period are prolonged, a large amount of alkaline substances and water resources are needed to be added, and the excessive; in addition, the alkali washing waste liquid can be discharged after being treated, and the treatment cost is high. In other reports, a solid catalyst is selected, the catalyst is filtered and removed after the esterification reaction, and then the excess (meth) acrylic acid is recovered by reduced pressure distillation, which has very high requirements on equipment and high energy consumption.
The esterification reaction is carried out according to the existing control conditions, after the esterification reaction is finished, the catalyst is recovered by cooling and filtering means, the polymerization inhibitor is recovered by washing, and then the epoxide is reacted with the (methyl) acrylic acid, so that the waste of the (methyl) acrylic acid can be avoided, alkaline washing is not needed, no waste liquid is generated, the requirement on equipment is not high, and the method has a very wide application prospect.
The distillation is generally carried out under negative pressure.
Preferably, the distillation pressure is 2 to 70 Kpa.
More preferably, the distillation pressure is 3 to 50 Kpa.
Most preferably, the distillation pressure is 5 to 15 Kpa.
Preferably, the distillation temperature is 40-100 ℃.
More preferably, the distillation temperature is 60-80 ℃.
The inert gas or oxygen-containing gas may be introduced into the distillation apparatus during the distillation.
Preferably, the oxygen-containing gas is air, or a mixture of air and nitrogen (lean air).
The amount of the inert gas or the oxygen-containing gas introduced is 0.1 to 1 m3/m3H, preferably 0.2 to 0.8 m3/m3H and more preferably 0.3 to 0.7 m3/m3H, based on the volume of the reaction mixture.
Preferably, the device selected in the distillation is a distillation device, a falling film or a thin film evaporator.
More preferably, the epoxide in S3 is one or more of a monomeric epoxide or a polymeric epoxide.
Epoxides generally have an average of at least 1 epoxy group per molecule which is reactive with a carboxyl group and can be aliphatic, cycloaliphatic, aromatic, or heterocyclic.
More preferably, the monomeric epoxy compound is epichlorohydrin, cyclohexene oxide, 1, 2-epoxy-4-vinylcyclohexane, methyl 3, 4-epoxycyclohexanecarboxylate, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, 3, 4-epoxycyclohexyl acrylate, 3, 4-epoxy ringHexyl methacrylate, glycidyl Tert-carbonate, allyl glycidyl Ether, isopropyl glycidyl Ether, butyl glycidyl Ether, octyl glycidyl Ether, decyl glycidyl Ether, C8-C10Alkyl glycidyl ethers, C12Alkyl glycidyl ethers, C12-C14One or more of alkyl glycidyl ether, phenyl glycidyl ether, o-tolyl glycidyl ether, benzyl glycidyl ether or p-tertiary phenyl glycidyl ether.
Preferably, the polymeric epoxide is one or more of polymeric aromatic epoxy compound, polymeric alicyclic epoxy compound, polymeric aliphatic epoxy compound or polymeric heterocyclic epoxy compound.
More preferably, the polymerization type aromatic epoxy compound is one or more of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol-Novolak type epoxy resin or cresol-Novolak type epoxy resin;
the polymerization type aliphatic epoxy compound is one or more of neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, propoxylated glycerol triglycidyl ether or pentaerythritol tetraglycidyl ether;
the polymerized alicyclic epoxy compound is one or more of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, diglycidyl hexahydrophthalate or diglycidyl methyltetrahydrophthalate;
the polymeric heterocyclic epoxy compound is one or more of hydantoin epoxy resin, triglycidyl isocyanurate or tetraglycidyl glycoluril.
Both monomeric epoxy compounds and polymeric epoxides, either presently disclosed or commercially available, may be used in the present invention.
Specifically, for example, CYD-128, CYD-118 (the tomb petrochemical), DER-331, DER-332, DER-324 (the Dow Chemical company), NPEL-128, NPEL-127 (the south Asia resin), JER828 (the Mitsubishi Chemical company), Araldite GY-240, Araldite GY-250 (the Hexion Specialty Chemicals, Inc), etc.; trimethylolpropane triglycidyl ether, diglycidyl ether of neopentyl glycol, and the like, such as XY-636, XY-633, XY-634 (New distal technologies, Anhui), HELOXYM DIFIER 48, HELOXY 68(Hexion Specialty Chemicals, Inc), and the like.
The amount of epoxide used is related to the amount of unreacted (meth) acrylic acid esterified, and the ratio of epoxide equivalent to (meth) acrylic acid equivalent is generally 1:0.80 ~ 1.3.3.
Under the condition of the dosage, the (methyl) acrylic acid can be completely reacted.
Preferably, the reaction temperature is 85-125 ℃.
More preferably, the reaction temperature is 95-110 ℃.
After the reaction is finished, the catalyst b and the polymerization inhibitor 2 can be recycled according to the requirement of impurity control.
Preferably, the tertiary amine is one or more of N, N-dimethylaniline, benzylamine, 4-lutidine or triethylamine.
Preferably, the quaternary ammonium salt is one or more of tetramethylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium chloride and triethylbenzylammonium bromide.
Preferably, the sulfonic acid is one or more of methane sulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid.
Preferably, the phosphine is one or more of triphenylphosphine, tributylphosphine, tricyclohexylphosphine or tri-tert-butylphosphine.
Preferably, the phosphonium salt is one or more of tetrabutylphosphonium chloride or tetrabutylphosphonium bromide.
Preferably, the metal halide is one or more of lithium chloride, lithium bromide, stannous chloride or zinc chloride.
Preferably, the metal organic compound is one or more of triphenylantimony, methyl triphenylantimony, chromium 2-ethylhexanoate, chromium octoate, zinc 2-ethylhexanoate, zinc octoate and zirconium octoate.
Preferably, the polymerization inhibitor 2 is one or more of 4-Methoxyphenol (MEHQ), p-tert-butylcatechol, tert-butylhydroquinone, o-methylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-p-cresol and methylhydroquinone.
Compared with the prior art, the invention has the following beneficial effects:
the research of the inventor of the invention finds that the 2-acrylamide-2-methylpropanesulfonic acid AMPS can be used as a catalyst for catalyzing esterification reaction, and has good catalytic activity and high yield. When the catalyst is applied to the preparation of (methyl) acrylate substances, the process is simple, the catalytic effect is good, and 2-acrylamide-2-methylpropanesulfonic acid and (methyl) acrylic acid are dissolved mutually in the esterification process, so that the esterification is favorably carried out. In addition, the solubility of the 2-acrylamide-2-methylpropanesulfonic acid at a lower temperature is lower, the temperature is reduced and the 2-acrylamide-2-methylpropanesulfonic acid is cooled after the esterification reaction, and the 2-acrylamide-2-methylpropanesulfonic acid is crystallized and separated out due to the reduction of the solubility, and can be recycled by filtration and separation.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
This example provides a method for preparing a trimethylolpropane triacrylate composition, which comprises the following steps.
In a 1000 mL four-mouth reaction flask, electric stirring, a thermometer, an LZB-2 type glass rotameter and a water separator (connected with a condenser) are added, 228g of trimethylolpropane, 400g of acrylic acid, 112g of heptane, 28g of toluene, 32g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 1.3g of cuprous chloride, 1.0g of 4-methoxyphenol and 3.5g of hypophosphorous acid are sequentially added, 1.8-2.5 mL/min of air is introduced, heating is carried out until the esterification reaction is in a reflux state, water generated by the azeotropic reaction of toluene and heptane is taken out of an esterification reaction bottle through the water separator until the water generated per hour is less than 1 mL and the temperature of the reaction solution is stable, and the temperature is taken as the end point of the esterification reaction. Cooling the esterification reaction mixture to below 40 ℃, adding 200g of toluene, and filtering; and washing the esterification reaction mixture for three times by 96.2g (containing 8.9 percent of acid) of acid generated in the esterification reaction at the washing temperature of 55-60 ℃.
And then evaporating the solvent at 1340KPa and 60-85 ℃. The reaction mixture obtained was 531g, the acid value was 35.2 mgKOH/g, and the yield was 95.3% (based on the alcohol, the same applies hereinafter).
The reaction mixture may be subjected to further processing:
in a 1000 ml four-mouth reaction flask, stirring electrically, heating with a thermometer, a reflux condenser and a constant temperature oil bath, adding 531g of esterification reaction mixture with an acid value of 35.2 mgKOH/g, adding 63g of CYD-128 epoxy resin (ba Ling petrochemical), 2.8g of triphenylphosphine and 1.0g of 4-methoxyphenol, reacting at 90-110 ℃ until the acid value is less than 3.0 mgKOH/g, and stopping the reaction.
Further, 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) obtained by filtration was used for the 2 nd time under the same conditions to catalyze the esterification reaction, whereby 542g of a reaction mixture was finally obtained, which had an acid value of 51.2 mgKOH/g and a yield of 92.2%.
The above steps are repeated, and the filtered 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) is utilized for the 3 rd time according to the same conditions to catalyze the esterification reaction, so that 548g of a reaction mixture is finally obtained, the acid value is 59.5 mgKOH/g, and the yield is 90.5%.
Example 2
This example provides a method for preparing a tripropylene glycol diacrylate composition which comprises the following steps.
In a 1000 mL four-mouth reaction flask, electric stirring, a thermometer and a water separator (connected with a condenser) are added, 342g of tripropylene glycol, 270g of acrylic acid, 128g of toluene, 18g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 2.8g of copper sulfate pentahydrate, 1.0g of 4-methoxyphenol, 3.9g of hypophosphorous acid and 1.0g of triphenylphosphine are sequentially added, the mixture is heated until the esterification reaction is in a reflux state, and the water generated by the reaction is taken out of the esterification reaction flask through the water separator by the azeotropic boiling of the toluene and the water until the water generated by the reaction is less than 1 mL per hour and the temperature of the reaction solution is stable, which is taken as the end point of the esterification reaction. Cooling the esterification reaction mixture to below 40 ℃, adding 220g of toluene, and filtering; and washing the esterification reaction mixture for three times by 64.7g (containing 6.3 percent of acid) of acid generated in the esterification reaction at the washing temperature of 40-55 ℃.
And then evaporating the solvent at the temperature of between 60 and 85 ℃ under the condition of 13 to 40 KPa. 526g of a reaction mixture was obtained, which had an acid value of 12.2 mgKOH/g and a yield of 94.6%.
The reaction mixture may be subjected to further processing:
in a 1000 ml four-mouth reaction flask, electric stirring, a thermometer, a reflux condenser and a constant temperature oil bath are carried out, 526g of esterification reaction mixture with the acid value of 12.2 mgKOH/g, 10.9g of epoxy chloropropane, 1.5g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and 1.0g of 4-methoxyphenol are added, and the reaction is stopped at the temperature of 85-100 ℃ until the acid value is less than 5.0 mgKOH/g.
Example 3
This example provides a method for preparing a propoxylated (5 PO) pentaerythritol tetraacrylate composition comprising the following steps.
In a 1000 mL four-mouth reaction flask, electric stirring, a thermometer, an LZB-2 type glass rotameter and a water separator (connected with a condenser) are added, 320g of propylene oxide (5 PO) pentaerythritol, 246g of acrylic acid, 160g of toluene, 36g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 1.5g of cuprous oxide, 0.9g of copper dibutyldithiocarbamate, 1.6g of 4-methoxyphenol and 5.2g of phosphorous acid are sequentially added, 2.8-3.5 mL/min of air is introduced, heating is carried out until the esterification reaction is in a reflux state, the water generated by the reaction is taken out of an esterification reaction bottle through the water separator by azeotropic boiling the toluene and the water until the water generated per hour is less than 1 mL and the temperature of the reaction liquid is stable, and the temperature is taken as the end point of the esterification reaction. Cooling the esterification reaction mixture to below 40 ℃, adding 200g of toluene, and filtering; washing the esterification reaction mixture for three times by using 59.3g (containing 10.3 percent of acid) of acid generated in the esterification reaction, wherein the washing temperature is 40-55 ℃. 886g of the reaction mixture was obtained, having an acid value of 16.7mgKOH/g and a yield of 98.3%.
The reaction mixture may be subjected to further processing:
in a 1000 ml four-mouth reaction flask, stirring electrically, heating with a thermometer, a reflux condenser, and heating in a constant temperature oil bath, 600g of esterification reaction mixture (containing solvent) with an acid value of 16.7mgKOH/g, 37.2g of pentaerythritol tetraglycidyl ether, 2.5g of triphenylphosphine, and 1.6g of 4-methoxyphenol are added, and the reaction is terminated at 90-115 ℃ until the acid value is less than 5.0 mgKOH/g.
And then evaporating the solvent at the temperature of between 60 and 90 ℃ under the condition of between 13 and 55 KPa.
Example 4
This example provides a method for preparing a tetrahydrofurfuryl methacrylate composition, comprising the following steps.
In a 1000 mL four-mouth reaction flask, electric stirring, a thermometer, an LZB-2 type glass rotameter, a water separator (connected with a condenser) and a vacuum system are distributed, 300g of tetrahydrofurfuryl alcohol, 286g of methacrylic acid, 180g of toluene, 18g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 5.6g of copper acrylate and 0.3g of hypophosphorous acid are sequentially added, 2.6-3.2 mL/min of air is introduced, heating is carried out until the esterification reaction is in a reflux state, water generated by the reaction is taken out of an esterification reaction bottle through the water separator until the water generated per hour is less than 1 mL and the temperature of the reaction liquid is stable, and the water is used as the end point of the esterification reaction. Cooling the esterification reaction mixture to below 40 ℃, adding 200g of toluene, and filtering; washing the esterification reaction mixture for three times by using 54.5g of acid water (containing 3.7 percent of acid) generated in the esterification reaction, wherein the washing temperature is 40-55 ℃. 910g of a reaction mixture was obtained, the acid value was 23.3mgKOH/g, and the yield was 99.2%.
The reaction mixture may be subjected to further processing:
in a 1000 ml four-mouth reaction flask, stirring, heating by a thermometer, a reflux condenser and a constant temperature oil bath kettle, adding 910g of esterification reaction mixture with an acid value of 23.3mgKOH/g, adding 37.0g of cyclohexene oxide, 1.7g of triethyl benzyl ammonium chloride, 1.7g of triethylamine and 0.9g of 4-methoxyphenol, reacting at 90-115 ℃ until the acid value is less than 3.0 mgKOH/g, and stopping the reaction.
And then evaporating the solvent at the temperature of between 60 and 90 ℃ under the condition of between 13 and 55 KPa.
While the foregoing is directed to particular example embodiments of the present invention, numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present invention. Rather, the scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

  1. The application of 2-acrylamide-2-methylpropanesulfonic acid AMPS as a catalyst in esterification reaction;
    the method is characterized in that raw materials of the esterification reaction are alcohols and monounsaturated acid;
    the alcohol is monohydric alcohol or polyhydric alcohol; the monounsaturated acid is (meth) acrylic acid;
    the temperature of the esterification reaction is 70-130 ℃; when the alcohol is monohydric alcohol, the equivalent ratio of the hydroxyl equivalent in the alcohol to (methyl) acrylic acid is 1: 1.1-1.5; when the alcohols are polyols, the equivalent ratio of hydroxyl equivalent in the alcohols to (methyl) acrylic acid is 1: 0.8-1.3;
    cooling to below 40 ℃ after esterification reaction, crystallizing and separating out 2-acrylamide-2-methylpropanesulfonic acid due to reduced solubility, and recycling after filtration and separation.
  2. 2. Use according to claim 1, wherein the monoalcohol is lauryl alcohol, C8-C10Alcohol, isooctanol, isodecanol, tetrahydrofuryl alcohol, cyclotrimethylolpropane formal, o-phenylphenoxy ethanol, 2- (2-hydroxyethoxy) phenol, diethylene glycol monoethyl ether, ethoxyethoxyethanol, ethoxynonylphenolOne or more of the above;
    the polyhydric alcohol is ethylene glycol, neopentyl glycol, 1, 3-propanediol, 1, 6-hexanediol, 2-ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol (methyl propanediol), dipropylene glycol, tripropylene glycol, ethoxylated neopentyl glycol, propoxylated neopentyl glycol, ethoxylated-1, 6-hexanediol, 1, 4-butanediol, diethylene glycol, triethylene glycol, ethoxylated bisphenol A, propoxylated bisphenol A, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, diethylene glycol phthalate, polyethylene glycol, polypropylene glycol, polyester diol, polytetrahydrofuran diol, polycaprolactone diol, trimethylolpropane, trimethylolethane, ethoxylated trimethylolpropane, ethylene glycol, propylene glycol, one or more of trimethylolpropane propoxylate, glycerol, ethoxylated glycerol, glycerol propoxylate, tris (2-hydroxyethyl) isocyanuric acid, tris (hydroxypropyl) isocyanuric acid, ethoxylated isocyanuric acid, propoxylated isocyanuric acid, caprolactone chain-extended ethoxylated isocyanuric acid, polyester triol, ditrimethylolpropane, ethoxylated ditrimethylolpropane, trimethylolpropane propoxylate, caprolactone chain-extended ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, pentaerythritol propoxylate, caprolactone chain-extended pentaerythritol, polyester tetraol, dipentaerythritol, ethoxylated dipentaerythritol, dipentaerythritol propoxylate, caprolactone chain-extended dipentaerythritol, polyester hexaol or hyperbranched polyester polyol.
  3. 3. A preparation method of (methyl) acrylate is characterized by comprising the following steps:
    taking alcohols and (methyl) acrylic acid as raw materials, taking 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) as a catalyst, and adding a polymerization inhibitor and a solvent for esterification reaction to obtain the (methyl) acrylate substances;
    the temperature of the esterification reaction is 70-130 ℃; when the alcohol is monohydric alcohol, the equivalent ratio of the hydroxyl equivalent in the alcohol to (methyl) acrylic acid is 1: 1.1-1.5; when the alcohol is a polyhydric alcohol, the equivalent ratio of the hydroxyl equivalent in the alcohol to (meth) acrylic acid is 1:0.8 to 1.3.
  4. 4. The production process according to claim 3, wherein the polymerization inhibitor is hydroquinone HQ, 4-methoxyphenol MEHQ, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2, 6-dimethylphenol, 2, 5-di-tert-butylphenol; one or more of copper chloride, cuprous chloride, copper oxide, cuprous oxide, basic copper carbonate, copper sulfate, copper acetate, acrylic acid ketone, copper methacrylate, copper salicylate, copper naphthenate, copper acetylacetonate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, cobalt acetate, cobalt carbonate, manganese acetate, manganese carbonate, manganese chloride, manganese sulfate, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, dibutyl phosphite, tricyclohexyl phosphite, hypophosphorous acid or phosphorous acid; the solvent is one or more of toluene, cyclohexane, n-hexane, methylcyclohexane, heptane or petroleum ether.
  5. 5. The method according to claim 3, wherein the esterification reaction process further comprises a step of performing dehydration treatment to obtain acid water and a solvent, and returning the solvent to the system of the esterification reaction.
  6. 6. The preparation method according to claim 3, characterized in that the esterification reaction is finished and the method further comprises cooling, filtering and recovering the catalyst; washing with water to recover the polymerization inhibitor.
  7. 7. The method according to claim 3, further comprising a step of recovering the solvent by distillation after the esterification reaction is completed.
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CN102500416A (en) * 2011-10-13 2012-06-20 北京化工大学 Synthesis and preparation methods of polymer particle type esterification catalyst containing sulfonic acid groups

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DE10116252A1 (en) * 2001-03-31 2002-10-02 Horst Kunz New 2-aryl-2-triorganylsilylether compounds useful for the solid phase synthesis of peptides and peptide conjugates, may be cleaved from the solid phase substrate under practically neutral conditions
WO2004000248A2 (en) * 2002-06-21 2003-12-31 Henkel Kommanditgesellschaft Auf Aktien Thickened cosmetic composition
CN102500416A (en) * 2011-10-13 2012-06-20 北京化工大学 Synthesis and preparation methods of polymer particle type esterification catalyst containing sulfonic acid groups

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